This study presents a novel visible light-active TiO2 nanotube anode film by sensitization with Bi2O3 nanoparticles. The uniform incorporation of Bi2O3 contributes to largely enhancing the solar light absorption and photoelectric conversion efficiency of TiO2 nanotubes. Due to the energy level difference between Bi2O3 and TiO2, the built-in electric field is suggested to be formed in the Bi2O3 sensitized TiO2 hybrid, which effectively separates the photo-generated electron-hole pairs and hence improves the photocatalytic activity. It is also found that the photoelectric conversion efficiency of Bi2O3 sensitized TiO2 nanotubes is not in direct proportion with the content of the sensitizer, Bi2O3, which should be carefully controlled to realize excellent photoelectrical properties. With a narrower energy band gap relative to TiO2, the sensitizer Bi2O3 can efficiently harvest the solar energy to generate electrons and holes, while TiO2 collects and transports the charge carriers. The new-type visible light-sensitive photocatalyst presented in this paper will shed light on sensitizing many other wide-band-gap semiconductors for improving solar photocatalysis, and on understanding the visible light-driven photocatalysis through narrow-band-gap semiconductor coupling.